CN115072989A - Optical glass and optical element - Google Patents
Optical glass and optical element Download PDFInfo
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- CN115072989A CN115072989A CN202210223455.4A CN202210223455A CN115072989A CN 115072989 A CN115072989 A CN 115072989A CN 202210223455 A CN202210223455 A CN 202210223455A CN 115072989 A CN115072989 A CN 115072989A
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- 239000005304 optical glass Substances 0.000 title claims abstract description 33
- 230000003287 optical effect Effects 0.000 title claims abstract description 26
- 230000005484 gravity Effects 0.000 claims abstract description 44
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 33
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 description 83
- 238000004031 devitrification Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical class OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000004554 molding of glass Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to an optical glass and an optical element. [ problem ] to]Provided are an optical glass and an optical element which have a low specific gravity with respect to the refractive index and yet have high stability. [ solving means]An optical glass comprising Ln in mass% based on oxides 2 O 3 The component (Ln) is 10.0% or less (more than 1 selected from La, Y, Gd and Yb), and the mass ratio of TiO 2 A ratio of 0.5 to 1.5 (R is at least 1 selected from the group consisting of Mg, Ca, Sr and Ba), and a total mass of Nb 2 O 5 +WO 3 +Bi 2 O 3 18.0% or less, a mass ratio BaO/RO of 0.30 to 0.95, a specific gravity d, and a refractive index n d When d is less than or equal to 6.17 Xn d -7.694.
Description
Technical Field
The present invention relates to an optical glass and an optical element.
Background
Optical glasses and optical elements can be used for applications in which optical characteristics of cameras, imaging devices, and the like are improved by combining lenses in different optical fields, applications in which various optical designs are realized by mounting the optical glasses and the optical elements in optical devices, and the like.
In particular, the weight reduction of optical glass and optical elements is associated with the reduction of the size and weight of optical device bodies, modules, and the like. For example, in an imaging apparatus such as a digital camera, in which chromatic aberration correction can be realized by combining a plurality of lenses and also a zoom function and an autofocus function are provided, a light optical element makes power transmission between an actuator and a lens smoother, and performance can be improved.
On the other hand, as glasses having a high refractive index, La-based glasses described in patent document 1 and P-Nb-based glasses described in patent document 2 are known, and inventions focusing on weight reduction of optical devices are described in patent documents 3 and 4.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-035037
Patent document 2: japanese patent laid-open No. 2012-171848
Patent document 3: WO2018/235725 publication
Patent document 4: japanese patent laid-open publication No. 2006-
Disclosure of Invention
Problems to be solved by the invention
The glass disclosed in patent document 1 contains a large amount of rare earth oxide having a higher specific gravity than other components; in patent document 2, the content of Nb that increases the specific gravity is large in the component having the high refractive index action.
Examples of the component having a large refractive index-increasing effect include rare earth oxide and TiO 2 Component (B) Nb 2 O 5 Component (I) and WO 3 Component (B) Bi 2 O 3 And (3) components.
When an optical glass having a high refractive index is desired, the content of the above-mentioned components needs to be increased, but the above-mentioned components are components each having a higher specific gravity than other components. Among the above components, TiO stands for 2 The component is the component with the smallest specific gravity, but TiO 2 The component has a low specific gravity, but is a component which impairs stability and is liable to cause devitrification.
When glass is produced, the content of the component for increasing the refractive index is increased, and the specific gravity tends to be increased as the refractive index is higher.
Since the glass disclosed in patent document 3 has a large specific gravity relative to the refractive index, it cannot be said that the optical glass is sufficiently light-weighted. Further, the glass disclosed in patent document 4 aims to: by modulating the refractive index (n) d ) When Y and the specific gravity of the glass are X, Y is equal to or more than 0.175X +1.137, and the glass with low specific gravity relative to the refractive index is obtained.
The present invention has been made in view of the above problems, and an object of the present invention is to obtain a glass having a low specific gravity with respect to a refractive index and high stability.
Means for solving the problems
The present inventors have conducted extensive experimental studies to solve the above problems, and as a result, have found that: by suppressing rare earth oxides and Nb 2 O 5 Component (I) and WO 3 Component (B) Bi 2 O 3 Content of the component and adjustment of TiO 2 The content of component and RO component, and the specific gravity is d and the refractive index is n d When d is less than or equal to 6.17 Xn d 7.694, thereby obtaining a glass having a low specific gravity with respect to the refractive index but high stability, and the present invention has been completed.
Specifically, the present invention provides the following inventions.
(1) An optical glass comprising, in mass% on an oxide basis,
Ln 2 O 3 the content of component (Ln is more than 1 selected from La, Y, Gd and Yb) is less than 10.0%,
mass ratio of TiO 2 The ratio of the acid to the acid is 0.5 to 1.5 (R is 1 or more selected from the group consisting of Mg, Ca, Sr and Ba),
sum of mass Nb 2 O 5 +WO 3 +Bi 2 O 3 The content of the organic acid is below 18.0%,
a mass ratio BaO/RO of 0.30 to 0.95,
d is specific gravity and n is refractive index d When the temperature of the water is higher than the set temperature,
d is less than or equal to 6.17 multiplied by n d -7.694.
(2) The optical glass according to the item (1), wherein the glass composition further comprises, in mass% on an oxide basis,
Nb 2 O 5 0 to 18.0 percent of component,
WO 3 0 to 15.0 percent of components,
La 2 O 3 The content of the components is 0-10.0%.
(3) The optical glass according to (1) or (2), wherein the total content of RO components is 20.0% or more.
(4) An optical element comprising the optical glass according to any one of (1) to (3).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an optical glass and an optical element having a low specific gravity with respect to the refractive index and high stability can be provided.
Drawings
FIG. 1 shows a glass composition containing a glass having a specific gravity d and a refractive index n according to an example of the present application d When d is less than or equal to 6.17 Xn d Expression of relation of-7.694, and refractive index (n) described in patent document 4 d ) An expression representing the relationship of Y.gtoreq.0.175X +1.137 when Y is used and the specific gravity of the glass is X (hereinafter, Y.gtoreq.0.175X +1.137 may be mentioned. ) Is shown in (a). The symbols shown in FIG. 1 are examples 11, 13, 19 and 22 of Japanese patent laid-open No. 2006-219365 (patent document 4).
FIG. 2 is a graph showing glasses relating to examples of the present application, in which the specific gravity is d and the refractive index is n d Graph of the relationship of time.
Detailed Description
The following describes in detail embodiments of the optical glass of the present invention. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although descriptions may be omitted as appropriate for overlapping descriptions, the present invention is not limited to the above description.
[ glass composition ]
The compositional ranges of the respective components constituting the optical glass of the present invention are described below. Unless otherwise specified, the content of each component in the present specification is represented by mass% of the total composition in terms of oxides with respect to the total substance amount of the glass. Here, the "oxide-reduced composition" means: when all of the oxides, complex salts, metal fluorides, and the like used as the raw materials of the glass constituent components of the present invention are decomposed into oxides during melting, the total mass of the formed oxides is defined as the composition of each component contained in the glass as 100 mass%.
SiO 2 The component (b) is a component which promotes the formation of stable glass by setting the content to 5.0% or more, thereby improving the devitrification resistance of the glass. In particular, by using SiO 2 The content of the component (B) is 35.0% or less, thereby suppressing the formation of SiO 2 A decrease in refractive index due to the composition. Thus, SiO 2 The upper limit of the content of the component (b) is preferably 35.0% or less, more preferably 33.0% or less, still more preferably 30.0% or less, still more preferably 28.0% or less, and most preferably 25.0% or less. On the other hand, SiO 2 The lower limit of the content of component (b) is preferably 5.0% or more, more preferably 6.0% or more, still more preferably 7.0% or more, and most preferably 8.0% or more.
TiO 2 The component (b) is a component whose refractive index and abbe number of the glass are increased by setting the content of the component (b) to 21.0% or more, and is an essential component of the present invention. On the other hand, by making TiO 2 The content of the component is 40.0% or less, and thus devitrification due to excessive content can be suppressed. Thus, TiO 2 The upper limit of the content of the component (B) is preferably 40.0% or less, more preferably 39.0% or less, and most preferably 38.0% or less. TiO 2 2 The lower limit of the content of component (c) is preferably 21.0% or more, more preferably 22.0% or more, still more preferably 23.0% or more, still more preferably 24.0% or more, and most preferably 25.0% or more.
Nb 2 O 5 When the content of the component (A) exceeds 0%, the refractive index and Abbe number of the glass are increased, and TiO 2 The components are contained together to improve stability. On the other hand, by using Nb 2 O 5 The content of the component (C) is 18.0% or less, and the specific gravity can be reduced to improve resistance to devitrification. Thus, Nb 2 O 5 The content of the component (C) is preferably 18.0% or lessMore preferably 15.0% or less, more preferably 12.0% or less, more preferably 11.0% or less, and most preferably 10.0% or less. On the other hand, from the viewpoint of improving stability, Nb 2 O 5 The lower limit of the content of component (c) is preferably 1.0% or more, more preferably 2.0% or more, further preferably 3.0% or more, further preferably 4.0% or more, and most preferably 5.0% or more, but may be 0%.
WO 3 Component (B) Bi 2 O 3 When the content of the component (b) exceeds 0%, the refractive index of the glass is increased, but when the content is large, the glass is colored and the specific gravity is increased. WO 3 Component (B) Bi 2 O 3 Preferred ranges of ingredients are as follows.
WO 3 The upper limit of the content of the component (b) is preferably 15.0% or less, more preferably 10.0% or less, more preferably 5.0% or less, more preferably 3.0% or less, and most preferably 1.0% or less.
Bi 2 O 3 The upper limit of the content of the component (b) is preferably 3.0% or less, more preferably 1.0% or less, further preferably 0.8% or less, further preferably 0.5% or less, further preferably 0.3% or less, and most preferably 0.1% or less.
B 2 O 3 The component (b) is a component which promotes the formation of stable glass and improves resistance to devitrification when the content exceeds 0%, and is an arbitrary component. In particular, by reacting B 2 O 3 The content of component (B) is 20.0% or less, thereby inhibiting B 2 O 3 The lowering of the refractive index by the component makes it possible to easily obtain a high refractive index. Thus, B 2 O 3 The upper limit of the content of the component (b) is preferably 20.0% or less, more preferably 17.0% or less, still more preferably 15.0% or less, and most preferably 12.0% or less. On the other hand, B 2 O 3 The lower limit of the content of the component (b) is preferably greater than 0%, more preferably 0.5% or more, further preferably 0.8% or more, and most preferably 1.0% or more, but may be 0%.
The BaO component is a component which improves the stability of the glass when it exceeds 0% and improves the workability during polishing and grinding. In particular, the specific gravity can be reduced by setting the content of the BaO component to 35.0% or less. Therefore, the upper limit of the content of the BaO component is preferably 35.0% or less, more preferably 33.5% or less, and most preferably 32.0% or less. On the other hand, the lower limit of the content of the BaO component is preferably 10.0% or more, more preferably 12.0% or more, further preferably 14.0% or more, and most preferably 15.0% or more.
The CaO component is a component which can reduce the specific gravity when it is contained in an amount exceeding 0%. In particular, by setting the content of the CaO component to 15.0% or less, the devitrification resistance can be improved. Therefore, the upper limit of the content of the CaO component is preferably 15.0% or less, more preferably 14.0% or less, and most preferably 13.0% or less. On the other hand, the lower limit of the content of the CaO component is preferably 0.5% or more, more preferably 1.0% or more, further preferably 2.0% or more, and most preferably 3.0% or more, but may be 0%.
The MgO component and the SrO component improve the devitrification resistance of the glass when they are contained in an amount exceeding 0%, but when they are contained in a large amount, it is difficult to maintain the refractive index and Abbe number. Preferred ranges of the MgO component and the SrO component are as follows.
The upper limit of the content of the MgO component is preferably 10.0% or less, more preferably 7.0% or less, further preferably 5.0% or less, and most preferably 3.0% or less, but may be 0%.
The upper limit of the content of the SrO component is preferably 10.0% or less, more preferably 7.0% or less, further preferably 5.0% or less, and most preferably 3.0% or less, but may be 0%.
La 2 O 3 Component (B) and (Y) 2 O 3 Component (b) Gd 2 O 3 Component Yb 2 O 3 The component (b) is a component which increases the refractive index of the glass when it exceeds 0%, reduces the abrasion amount of the glass during polishing, and hardly causes cracking or breakage of the glass, and deterioration of profile unevenness (profile uniformity), but when it exceeds 0%, stability is impaired and specific gravity becomes large. La 2 O 3 Component (B) and (Y) 2 O 3 Component (b) Gd 2 O 3 Component Yb 2 O 3 Preferred ranges of the components are as followsThe above-mentioned processes are described.
La 2 O 3 The upper limit of the content of the component (b) is preferably 10.0% or less, more preferably 8.0% or less, further preferably 5.0% or less, further preferably 3.0% or less, and most preferably 1.0% or less.
Y 2 O 3 The upper limit of the content of the component (b) is preferably 10.0% or less, more preferably 8.0% or less, further preferably 5.0% or less, further preferably 3.0% or less, and most preferably 1.0% or less.
Gd 2 O 3 The upper limit of the content of the component (b) is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less, and most preferably 0.5% or less.
Yb 2 O 3 The upper limit of the content of the component (b) is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.0% or less, still more preferably 1.0% or less, and most preferably 0.5% or less.
ZrO 2 The component (b) is an optional component, and when it exceeds 0%, it promotes the stable storage of the glass and improves the devitrification resistance of the glass. On the other hand, by using ZrO 2 The content of the component (b) is 10.0% or less, so that glass processing by grinding/polishing or the like can be easily performed. Thus, ZrO 2 The upper limit of the content of the component (b) is preferably 10.0% or less, more preferably 9.0% or less, still more preferably 8.0% or less, and most preferably 7.0% or less. On the other hand, ZrO 2 The content of the component (b) is preferably 0.1% or more, more preferably 0.2% or more, and further preferably 0.3% or more, but may be 0%.
Li 2 Component O and K 2 O component and Na 2 The O component is a component which lowers the melting temperature of the glass when it is contained in an amount exceeding 0%, but when it is contained in a large amount, stability is impaired and devitrification is liable to occur. Li 2 Component O and K 2 O component and Na 2 Preferable ranges of the O component are as follows.
Li 2 The content of the O component is preferably 7.0% or less, more preferably 5.0% or less, further preferably 3.0% or less, and most preferably 1.0% or lessThe lower limit is set as the upper limit.
K 2 The upper limit of the content of the O component is preferably 7.0% or less, more preferably 5.0% or less, still more preferably 3.0% or less, and most preferably 1.0% or less.
Na 2 The upper limit of the content of the O component is preferably 10.0% or less, more preferably 8.0% or less, further preferably 6.0% or less, and most preferably 4.0% or less. On the other hand, Na 2 The lower limit of the content of the O component is preferably 0.1% or more, more preferably 0.3% or more, and most preferably 0.5% or more, but may be 0%.
Al 2 O 3 The component (b) is a component which improves the chemical durability of the glass and increases the viscosity of the glass at the time of melting when the content exceeds 0%, and is an arbitrary component. In particular, by using Al 2 O 3 The content of the component (b) is 5.0% or less, whereby the glass is improved in meltability and reduced in devitrification tendency. Thus, Al 2 O 3 The upper limit of the content of the component (b) is preferably 5.0% or less, more preferably 3.0% or less, and most preferably 1.0% or less, but may be 0%.
The ZnO component is a component which lowers the liquidus temperature of the glass and improves the devitrification resistance of the glass when it exceeds 0%, and is an arbitrary component. In particular, by setting the content of the ZnO component to 5.0% or less, a high refractive index and low dispersion can be easily obtained. Therefore, the content of the ZnO component is preferably 5.0% or less, more preferably 3.0% or less, and most preferably 1.0% or less as an upper limit, but may be 0%.
Ta 2 O 5 The component (b) is a component which increases the refractive index of the glass by containing more than 0% of the glass and improves the devitrification resistance of the glass, and is an arbitrary component. On the other hand, by using Ta 2 O 5 The content of the component (A) is 5.0% or less, thereby reducing Ta as a rare mineral resource 2 O 5 The amount of the components is small, and the glass is easily melted at a lower temperature, so that the production cost of the glass can be reduced. In addition, Ta can be reduced thereby 2 O 5 The excess of ingredients contained the resulting devitrification of the glass. Thus, Ta 2 O 5 Of ingredientsThe upper limit of the content is preferably 5.0% or less, more preferably 3.0% or less, and further preferably 1.0% or less, but may be 0%.
P 2 O 5 The content of the component (b) is preferably 5.0% or less, more preferably 3.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less as an upper limit, but may be 0%.
The content of the component F is preferably 5.0% or less, more preferably 3.0% or less, more preferably 1.0% or less, further preferably 0.5% or less, further preferably 0.3% or less as an upper limit, but may be 0%.
TeO 2 The content of the component (b) is preferably 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less as an upper limit, but may be 0%.
GeO 2 The content of the component (b) is preferably 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less as an upper limit, but may be 0%.
CeO 2 The content of the component (b) is preferably 3.0% or less, more preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less as an upper limit, but may be 0%.
Er 2 O 3 Component (b) Pr 2 O 3 The content of the component (b) is preferably 1.0% or less, more preferably 0.5% or less, more preferably 0.1% or less, and most preferably substantially not contained.
SnO 2 The upper limit of the content of the component (b) is preferably 2.0% or less, more preferably 1.0% or less, and further preferably 0.5% or less, but may be 0%.
Sb 2 O 3 The component (b) is a component which promotes clarification and defoaming when melting glass, and is an arbitrary component. Here, by making Sb 2 O 3 The content of the component (A) is 0.1% or less, whereby coloring in the high refractive index glass can be suppressed. In addition, by setting the content to 0.1% or less, excessive foaming at the time of glass melting becomes less likely to occur, and therefore Sb can be made to be small 2 O 3 The components are not easy to be melted (especially precious gold such as Pt)Belongs to) alloying. Thus, Sb 2 O 3 The content of the component (b) is preferably 0.1% or less, more preferably 0.08% or less, and further preferably 0.05% or less as an upper limit, but may be 0%.
The components for clearing and degassing the glass are not limited to the above-mentioned Sb 2 O 3 As the component (b), a clearing agent, a defoaming agent, or a combination thereof, which is known in the art of glass production, can be used.
By mixing Ln 2 O 3 The total content (mass sum) of the components (Ln is 1 or more selected from the group consisting of La, Y, Gd, and Yb) is 10.0% or less, and thus devitrification due to excessive content can be suppressed and the specific gravity can be reduced. Therefore, the upper limit is preferably 10.0% or less, more preferably 9.0% or less, further preferably 6.0% or less, further preferably 4.0% or less, further preferably 2.0% or less.
By adding Rn 2 The total content of O components (Rn is 1 or more selected from the group consisting of Li, Na, and K in the formula) is 10.0% or less, and deterioration of reheat press formability can be suppressed. Thus, Rn 2 The total content of the O components is preferably 10.0% or less, more preferably 9.0% or less, and most preferably 8.0% or less as an upper limit. On the other hand, Rn is added to improve the melting property 2 The lower limit of the total content of the O components is preferably 0.5% or more, more preferably 0.8% or more, and further preferably 1.0% or more, but may be 0%.
When the total content of RO components (wherein R is 1 or more selected from the group consisting of Mg, Ca, Sr, and Ba) exceeds 0%, the stability of the glass can be improved. In particular, the RO component has a function of inhibiting the formation of TiO 2 The effect of ingredient-induced devitrification. The total content of RO components is preferably 20.0% or more, more preferably 21.5% or more, further preferably 23.0% or more, and most preferably 25.0% or more. On the other hand, in order to suppress the decrease in refractive index, the total content of RO components is preferably 40.0% or less, more preferably 39.0% or less, more preferably 38.0% or less, still more preferably 37.0% or less, and most preferably 36.0% or less as an upper limit.
By using as TiO 2 Ratio of component to RO component, i.e., mass ratio TiO 2 The amount of the catalyst component/RO is set to 0.50 or more and 1.50 or less, thereby making it possible to suppress the formation of TiO 2 Devitrification by the ingredients and high stability. The production of glass having high stability is useful for improving mass productivity. Therefore, mass ratio of TiO 2 The lower limit of/RO is preferably 0.50 or more, more preferably 0.55 or more, further preferably 0.60 or more, further preferably 0.65 or more, and most preferably 0.70 or more. On the other hand, mass ratio of TiO 2 The upper limit of/RO is preferably 1.50 or less, more preferably 1.45 or less, further preferably 1.40 or less, further preferably 1.35 or less, and most preferably 1.30 or less.
By using as Nb 2 O 5 Component (I) and WO 3 Component (B) Bi 2 O 3 Sum of the masses Nb of the total amounts of the components 2 O 5 +WO 3 +Bi 2 O 3 The specific gravity can be suppressed from increasing by setting the specific gravity to 18.0% or less. The component contributing to the high refractive index is large in specific gravity compared with other components, and Nb as the component contributing to the high refractive index is suppressed 2 O 5 Component (I) and WO 3 Component (B) Bi 2 O 3 The content of the component (a) can suppress an increase in specific gravity, and contributes to downsizing and weight reduction of an optical device. Therefore, the sum of masses Nb 2 O 5 +WO 3 +Bi 2 O 3 The upper limit is preferably 18.0% or less, more preferably 15.0% or less, more preferably 13.0% or less, further preferably 11.0% or less, further preferably 10.0% or less. On the other hand, the total mass Nb is from the viewpoint of improving the refractive index and dispersion 2 O 5 +WO 3 +Bi 2 O 3 May be 1.0% or more. Therefore, the sum of masses Nb 2 O 5 +WO 3 +Bi 2 O 3 It is preferably 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0% or more, or 6.0% or more.
By setting the mass ratio BaO/RO, which is the ratio of BaO component to RO component, to 0.30 or more and 0.95 or less, glass with high stability can be obtained. Particularly, the BaO component in the present invention is the most stable component in the RO component. Further, it is possible to prevent cracking and breakage of the glass during processing such as polishing and deterioration of profile unevenness. Therefore, the mass ratio BaO/RO is preferably 0.30 or more, more preferably 0.40 or more, further preferably 0.50 or more, and further preferably 0.55 or more as the lower limit. On the other hand, the mass ratio BaO/RO is preferably 0.95 or less, more preferably 0.93 or less, and further preferably 0.90 or less as an upper limit.
By using as Nb 2 O 5 Component to TiO 2 Mass ratio of component ratios Nb 2 O 5 /TiO 2 By setting the refractive index to 0.50 or less, the specific gravity can be reduced by increasing the refractive index. Mass ratio Nb 2 O 5 /TiO 2 The upper limit is preferably 0.50 or less, more preferably 0.48 or less, further preferably 0.45 or less, further preferably 0.42 or less, and most preferably 0.40 or less. On the other hand, to obtain the inhibited TiO 2 Mass ratio Nb from the viewpoint of devitrification due to the glass and high stability 2 O 5 /TiO 2 May be 0.05 or more. Therefore, mass ratio Nb 2 O 5 /TiO 2 The lower limit is preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.10 or more, and most preferably 0.13 or more.
By using as ZrO 2 Component to TiO 2 Component (B) and Nb 2 O 5 Mass ratio ZrO of ratio of total content of components 2 /(TiO 2 +Nb 2 O 5 ) Setting to 0.25 or less is effective in that the devitrification resistance can be improved. In contrast to TiO 2 Component (B) and Nb 2 O 5 Total content of component(s), ZrO 2 When the content of the component is too large, devitrification is caused. Mass ratio ZrO 2 /(TiO 2 +Nb 2 O 5 ) The upper limit is preferably 0.25 or less, more preferably 0.20 or less, and still more preferably 0.19 or less.
For as Nb 2 O 5 Component (A) and WO 3 The total content of the components relative to TiO 2 Component (B) and Nb 2 O 5 Component (I) and WO 3 Mass ratio of total content of components (Nb) 2 O 5 +WO 3 )/(TiO 2 +Nb 2 O 5 +WO 3 ) To suppress Nb 2 O 5 And WO 3 The increase in specific gravity due to the reaction is preferably 0.50 or less. Mass ratio (Nb) 2 O 5 +WO 3 )/(TiO 2 +Nb 2 O 5 +WO 3 ) Preferably 0.50 or less, more preferably 0.40 or less, further preferably 0.30 or less, and further preferably 0.28 or less. On the other hand, the mass ratio (Nb) is from the viewpoint of improving the refractive index and dispersion 2 O 5 +WO 3 )/(TiO 2 +Nb 2 O 5 +WO 3 ) May be 0.05 or more. Mass ratio (Nb) 2 O 5 +WO 3 )/(TiO 2 +Nb 2 O 5 +WO 3 ) The lower limit is preferably 0.05 or more, more preferably 0.07 or more, further preferably 0.08 or more, and further preferably 0.10 or more.
< ingredients not to be contained >
Next, components that should not be contained in the optical glass of the present invention and components that are not preferably contained therein will be described.
Other components may be added as necessary within a range not impairing the characteristics of the glass of the present invention. Among them, in addition to Ti, Zr, Nb, W, La, Gd, Y, Yb, and Lu, when each of the transition metal components such as Nd, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo is contained in a small amount alone or in combination, the glass is colored and absorbs a specific wavelength in the visible region, and therefore, it is preferable that the glass is not substantially contained in an optical glass using a specific wavelength in the visible region.
Further, lead compounds such As PbO and As 2 O 3 The arsenic compound is a component having a high environmental load, and therefore it is desired that the arsenic compound is not substantially contained, that is, not contained at all except for unavoidable impurities.
Further, in recent years, each component of Th, Cd, Tl, Os, Be, and Se tends to Be used restrictively as a harmful chemical substance, and measures against the environment are required not only in the glass production process but also in the processing process and the disposal after commercialization. Therefore, when the environmental influence is considered, it is preferable that these are not substantially contained.
[ Properties ]
Refractive index (n) of the optical glass of the present invention d ) Preferably 1.80500 or more, 1.81000 or more, 1.82000 or more, 1.83000 or more, 1.84000 or more, 1.85000 or more, 1.86000 or more, 1.87000 or more, 1.88000 or more, 1.89000 or more, 1.90000 or more in this order. On the other hand, the refractive index (n) d ) May be 2.00000 or less, 1.99000 or less, 1.98000 or less, 1.97000 or less, or 1.96000 or less. Abbe number (v) of the present invention d ) Preferably 17.00 or more, 18.00 or more, 19.00 or more, 20.00 or more, 21.00 or more in this order. On the other hand, the Abbe number (. nu.) d ) Preferably 30.00 or less, 28.00 or less, 27.00 or less, and 26.00 or less in this order.
The specific gravity (d) of the optical glass of the present invention is preferably 4.43 or less, 4.30 or less, 4.20 or less, 4.10 or less, and 4.05 or less in this order.
In addition to the above, the optical glass of the present invention preferably has a specific gravity (d) with respect to the refractive index (n) d ) D is less than or equal to 6.17 multiplied by n d -7.694. When glass is produced, the specific gravity of the component for increasing the refractive index is high in addition to other components, and therefore, the content of the component for increasing the refractive index tends to increase, and the specific gravity tends to increase as the refractive index increases. The inventor finds that: by satisfying d ≦ 6.17 xn d 7.694, thereby reducing the specific gravity with respect to the refractive index, becomes useful in optical design. Specific gravity (d) relative to refractive index (n) d ) Preferably d.ltoreq.6.17 Xn d The relationship of-7.694, more preferably d.ltoreq.6.17 Xn d A relationship of-7.800, further preferably satisfying d.ltoreq.6.17 Xn d -7.914。
As shown in fig. 1, it was confirmed that: when compared with the case where Y is not less than 0.175X +1.137 as described in patent document 4, d is not more than 6.17 Xn d The relationship of-7.694 is an expression representing a glass having a low specific gravity with respect to the refractive index.
[ production method ]
The optical glass of the present invention can be produced, for example, as follows. That is, the raw materials are uniformly mixed so that the respective components are within a predetermined content range, the obtained mixture is put into a platinum crucible, melted in an electric furnace at a temperature range of 1100 to 1500 ℃ for 2 to 5 hours depending on the degree of difficulty of melting of the glass raw material, stirred and homogenized, then cooled to an appropriate temperature, cast into a mold, and slowly cooled to manufacture the glass.
[ Molding of glass ]
The glass of the present invention can be melt-molded by a known method. The apparatus for molding the glass melt is not limited.
[ optical element ]
From the optical glass produced, an apparatus such as a grinding process is used; or a press molding apparatus such as reheat press molding or precision press molding, and a glass molding can be produced. That is, the glass molded body can be produced by subjecting the optical glass to mechanical processing such as grinding and polishing. The apparatus for producing the glass molded body is not limited to these apparatuses.
Thus, the optical glass of the present invention is useful for various optical elements and optical designs. Among them, optical elements such as lenses and prisms are particularly preferably produced. Thus, in addition to the reduction in weight of the optical element, when used in an optical apparatus such as a camera or a projector, high-definition and high-precision imaging characteristics and projection characteristics can be realized.
Examples
Compositions of examples and comparative examples of the glass of the present invention, and refractive indices (n) of these glasses d ) Abbe number (v) d ) Specific gravity (d), and 6.17 Xn d -7.694、6.17×n d -7.800、6.17×n d The values of-7.914 are shown in tables 1 and 2. Comparative example B is example 13 of WO 2018/235725.
The glasses of examples and comparative examples of the present invention were produced by selecting, as raw materials for each component, high-purity raw materials used in general optical glasses such as oxides, hydroxides, carbonates, nitrates, fluorides, metaphosphoric acid compounds, etc. corresponding to the raw materials, weighing the raw materials so as to have the composition ratios of the respective examples shown in the table, uniformly mixing the raw materials, putting the mixture into a platinum crucible, melting the mixture in an electric furnace at a temperature of 1100 to 1400 ℃ for 2 to 5 hours depending on the ease of melting of the glass raw materials, stirring the mixture to homogenize the mixture, casting the homogenized mixture into a mold, etc., and slowly cooling the homogenized mixture.
Refractive index (n) of glasses of examples and comparative examples d ) Abbe number (v) d ) According to JIS B7071-2: 2018 by the V-Block method. Here, the refractive index (n) d ) The measured value was expressed as d-line (587.56nm) relative to the helium lamp. In addition, for Abbe number (v) d ) Using the refractive index (n) of the d-line relative to the helium lamp d ) And a refractive index (n) with respect to an F line (486.13nm) of the hydrogen lamp F ) Refractive index (n) with respect to C line (656.27nm) C ) A value of (d) by Abbe number (v) d )＝[(n d -1)/(n F -n C )]And (4) calculating the formula. These refractive indices (n) d ) Abbe number (v) d ) The temperature was determined by measuring a glass obtained by setting the slow cooling rate to-25 ℃/hr.
The specific gravity in the glass of the examples is based on the specific gravity determined by JISZ 8807: 2012 in the liquid and measuring the density and specific gravity by the weighing method.
[ Table 1]
[ Table 2]
As shown in the table, the glasses of the examples of the present invention all have a refractive index (n) d ) 1.80500 or more, more specifically 1.85000 or more, and the refractive index (n) d ) The value is 2.00000 or less, more specifically 1.97000 or less, and is within a desired range.
For the practice of the inventionThe glasses of the examples are all Abbe number (. nu.) d ) 17.00 or more, more specifically 21.00 or more, and the Abbe number (. nu.) d ) Is 30.00 or less, more specifically 26.00 or less, and falls within a desired range.
The glasses of the examples of the present invention did not devitrify but were glasses having high stability. On the other hand, mass ratio of TiO 2 Comparative example A, in which the RO exceeded 1.50, underwent devitrification, and no vitrification was achieved.
The glasses of the embodiments of the invention all satisfy d ≦ 6.17 Xn d The relationship of-7.694, more particularly d.ltoreq.6.17 Xn d -7.800. On the other hand, as shown in FIG. 1, the glasses of examples 11, 13, 19, 22 of Japanese patent application laid-open No. 2006- d The relationship of-7.694 is inferior from the viewpoint of weight reduction of the product.
Thus, it was confirmed that: the optical glass of the embodiment of the present invention has a low specific gravity with respect to the refractive index and is a glass having high stability.
The present invention has been described in detail for the purpose of illustration, but it is to be understood that this embodiment is for illustrative purposes only and that various modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (4)
1. An optical glass comprising, in mass% on an oxide basis,
Ln 2 O 3 the component is 10.0% or less, wherein Ln is more than 1 selected from the group consisting of La, Y, Gd, and Yb,
mass ratio of TiO 2 The ratio of the acid groups to the acid groups/RO is 0.5 to 1.5, wherein R is 1 or more selected from the group consisting of Mg, Ca, Sr and Ba,
sum of mass Nb 2 O 5 +WO 3 +Bi 2 O 3 The content of the organic acid is below 18.0%,
a mass ratio BaO/RO of 0.30 to 0.95,
d is specific gravity and n is refractive index d When the temperature of the water is higher than the set temperature,
d is less than or equal to 6.17 multiplied by n d -7.694.
2. The optical glass according to claim 1, which is in mass% on an oxide basis,
Nb 2 O 5 0 to 18.0 percent of components,
WO 3 0 to 15.0 percent of components,
La 2 O 3 The component is 0-10.0%.
3. The optical glass according to claim 1 or 2,
the total content of RO components is 20.0% or more.
4. An optical element comprising the optical glass as defined in any one of claims 1 to 3.
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| JP2021038023A JP2022138242A (en) | 2021-03-10 | 2021-03-10 | Optical glass and optical element |
| JP2021-038023 | 2021-03-10 |
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| JP (1) | JP2022138242A (en) |
| CN (1) | CN115072989A (en) |
| TW (1) | TW202246192A (en) |
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